Transformation of Au144(SCH2CH2Ph)60 to Au133(SPh- t Bu)52 Nanomolecules: Theoretical and experimental study

Praneeth Reddy Nimmala; Shevanuja Theivendran; Giovanni Barcaro; Luca Sementa; Chanaka Kumara; Vijay Reddy Jupally; Edoardo Apra; Mauro Stener; Alessandro Fortunelli; Amala Dass

doi:10.1021/acs.jpclett.5b00780

Transformation of Au₁₄₄(SCH₂CH₂Ph)₆₀ to Au₁₃₃(SPh- t Bu)₅₂ Nanomolecules: Theoretical and experimental study

Praneeth Reddy Nimmala, Shevanuja Theivendran, Giovanni Barcaro, Luca Sementa, Chanaka Kumara, Vijay Reddy Jupally, Edoardo Apra, Mauro Stener, Alessandro Fortunelli, Amala Dass

Research output: Contribution to journal › Article › peer-review

57 Scopus citations

Abstract

Ultrastable gold nanomolecule Au₁₄₄(SCH₂CH₂Ph)₆₀ upon etching with excess tert-butylbenzenethiol undergoes a core-size conversion and compositional change to form an entirely new core of Au₁₃₃(SPh-tBu)₅₂. This conversion was studied using high-resolution electrospray mass spectrometry which shows that the core size conversion is initiated after 22 ligand exchanges, suggesting a relatively high stability of the Au₁₄₄(SCH₂CH₂Ph)₃₈(SPh-tBu)₂₂ intermediate. The Au₁₄₄ Au₁₃₃ core size conversion is surprisingly different from the Au₁₄₄ Au₉₉ core conversion reported in the case of thiophenol, SPh. Theoretical analysis and ab initio molecular dynamics simulations show that rigid p-tBu groups play a crucial role by reducing the cluster structural freedom, and protecting the cluster from adsorption of exogenous and reactive species, thus rationalizing the kinetic factors that stabilize the Au₁₃₃ core size. This 144-atom to 133-atom nanomolecule's compositional change is reflected in optical spectroscopy and electrochemistry.

Original language	English
Pages (from-to)	2134-2139
Number of pages	6
Journal	Journal of Physical Chemistry Letters
Volume	6
Issue number	11
DOIs	https://doi.org/10.1021/acs.jpclett.5b00780
State	Published - Jun 4 2015
Externally published	Yes

Funding

Funders	Funder number
National Science Foundation	1255519

Keywords

Au(SPh- t Bu) nanomolecules
and conjugating effects
core-size conversion
ligand replacement process

Access to Document

10.1021/acs.jpclett.5b00780

Cite this

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title = "Transformation of Au144(SCH2CH2Ph)60 to Au133(SPh- t Bu)52 Nanomolecules: Theoretical and experimental study",

abstract = "Ultrastable gold nanomolecule Au144(SCH2CH2Ph)60 upon etching with excess tert-butylbenzenethiol undergoes a core-size conversion and compositional change to form an entirely new core of Au133(SPh-tBu)52. This conversion was studied using high-resolution electrospray mass spectrometry which shows that the core size conversion is initiated after 22 ligand exchanges, suggesting a relatively high stability of the Au144(SCH2CH2Ph)38(SPh-tBu)22 intermediate. The Au144 Au133 core size conversion is surprisingly different from the Au144 Au99 core conversion reported in the case of thiophenol, SPh. Theoretical analysis and ab initio molecular dynamics simulations show that rigid p-tBu groups play a crucial role by reducing the cluster structural freedom, and protecting the cluster from adsorption of exogenous and reactive species, thus rationalizing the kinetic factors that stabilize the Au133 core size. This 144-atom to 133-atom nanomolecule's compositional change is reflected in optical spectroscopy and electrochemistry.",

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author = "Nimmala, {Praneeth Reddy} and Shevanuja Theivendran and Giovanni Barcaro and Luca Sementa and Chanaka Kumara and Jupally, {Vijay Reddy} and Edoardo Apra and Mauro Stener and Alessandro Fortunelli and Amala Dass",

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AU - Fortunelli, Alessandro

AU - Dass, Amala

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